Perfluorotricyclic amines as oxygen carriers

ABSTRACT

A novel compound of the formula, ##STR1## wherein k, j, l and m are zero or an integer of from 1 to 3, and n is an integer of from 1 to 3, the rings A, B and C being optionally substituted with at least one trifluoromethyl group, prepared by reacting the corresponding perhydro compound with fluorine is useful as a material capable of carrying oxygen in an aqueous emulsion for lifesaving a patient suffering from massive hemorrhage and for preserving internal organs in transplantation.

This invention relates to a novel perfluorotricyclic amine compounduseful as an oxygen carrier in artificial blood or in an infusion fluid.

More particularly, it relates to a perfluorotricyclic amine compoundrepresented by the general formula ##STR2## wherein k, j, l and m arezero or an integer of from 1 to 3, and n is an integer of from 1 to 3,the rings A, B and C being optionally substituted with at least onetrifluoromethyl group.

Regarding the general formula (I), it is preferable that the ring A isselected from five- to seven-membered rings, the ring B from five- toeight-membered rings, and the ring C from five- to eight-membered rings.The total number of the carbon atoms contained in the compound offormula (I) is preferably from 9 to 12.

In detail, the first series of the present perfluorotricyclic aminecompounds without optional substituent of --CF₃ is represented by theformula, ##STR3## wherein k is an integer of 1 or 2; l, m and n are zeroor an integer of 1 or 2. The compound has preferably 10 to 12 carbonatoms in total.

The second series is also represented by the formula, ##STR4## wherein kand n are an integer of 1, 2 or 3; l and m are zero or an integer of 1,2 or 3. The compound has preferably 10 to 12 carbon atoms in total.

The third series is also represented by the formula, ##STR5## wherein kand j are zero or an integer of 1; l, m and n are zero or an integer of1 or 2. The compound has preferably 10 to 12 carbon atoms in total.

The fourth series is also represented by the formula, ##STR6## wherein land m are zero or an integer of 1, 2 or 3; n is an integer of 1, 2 or 3.

The compound may have at most two trifluoromethyl groups and its totalnumber of carbon atoms are preferably 9 to 12 in case of no substituentand 10 to 11 depending on the substituted number of the trifluoromethylgroup.

The compound of formula (I) can be prepared by fluorinating aperhydro-compound corresponding to the compound of formula (I). Themethods of fluorination include, for example, a direct fluorination, afluorination by use of cobalt trifluoride, and an electro chemicalfluorination.

The preparation of the compound of formula (I) of this invention ispreferably performed by the electrochemical fluorination method. This isperformed, for example, by mixing anhydrous hydrogen fluoride and theperhydro-compound used as the starting compound in an electrolytic celland subjecting the resulting solution to electrolysis. The voltage, thecurrent density at the anode, and the temperature of electrolyticsolution are normally 3-9 V, 0.1-10 A/dm² and 4°-12° C., respectively.

The compound of formula (I) thus formed was drained from the bottom ofthe cell, being insoluble in anhydrous hydrogen fluoride.

The isolation and purification of the compound from the drained productare carried out, for example, by adding a mixture of equal volumes of anaqueous caustic alkaline solution and an amine compound to the drainedproduct and refluxing to decompose partially fluorinated compounds.After cooled, the lowermost layer containing the desired compound offormula (I) is separated, washed with an aqueous acetone solutioncontaining a suitable amount of potassium iodide to removeperfluoroalkyl nitrogen fluorides, and subjected to fractionaldistillation to obtain the fraction of the desired compound of formula(I).

Since the compound of the formula (I) of this invention can not onlydissolve a large amount of oxygen, and is chemically and biologicallyinert, but also it can be excreted rapidly from the body, it can form,for example, an aqueous emulsion containing 5 to 50, preferably 10-40, %(W/V) of the compound of formula (I) to be used as an oxygen carrier inan artificial blood or in an infusion liquid for men and other mammalssuch as dogs, cats, cattle, mice, rats and guinea pigs.

The symbol "%(W/V)" referred to herein mean the amount of the materialby weight (gram) based on 100 ml of the resulting emulsion.

In the preparation of the emulsion mentioned above, there used, as anemulsifier, a nonionic surfactant and/or phospholipids in an addedamount of 1 to 5% (W/V).

As the medium for the emulsion, a physiologically acceptable aqueoussolution is employed. If necessary, there may be added thereto suchmaterials as glycerol to provide the desired isotonicity, and suchplasma expanders as HES or dextran to regulate the colloid osmoticpressure of the emulsion.

The emulsion can be prepared by mixing the above-mentioned ingredientsand homogenizing the mixture by means of, for example, a high-pressurejet type homogenizer until the particle diameters become 0.05 to 0.3 μm,preferably less than 0.2 μm.

The perhydro-compounds (starting compounds) corresponding to thecompounds of formula (I) are substantially known already.

EXAMPLE 1

Into an electrolytic cell made of Monel metal with an inner volume of1.5 l, which is provided with electrode plates (six plates as anode andseven plates as cathode) made of nickel (purity: 99.6% or higher)arranged alternately with an inter-electrode distance of 1.7-2.0 mm, theeffective anode surface area being 10.5 dm², and with a reflux condensermade of copper at the upper part of the cell, was introduced 1.2 l ofanhydrous hydrogen fluoride, and trace amounts of impurities present inthe system (moisture and sulfuric acid) were removed by preliminaryelectrolysis. Then, 0.86 mol (130 g) of 2-azatricyclo[5,3,1,0²,6]-undecane was dissolved into the anhydrous hydrogen fluoride, andelectrolysis was carried out, while introducing helium gas from thebottom of the cell at a rate of 100 ml/min., under the conditions ofanode current density of 0.4-2.0 A/dm², voltage of 5-9 V and solution7°-12° C., until the electrolytic voltage had reached 9.0 V. Theampere-hours amounted to 975. Hydrogen fluoride was added at a rate of250 ml per 24 hours during the electrolysis. No attempt was made tocollect volatile products formed by a bond breaking reaction, whichwould give more yields of the desired product. After completion of theelectrolysis, fluorocarbons in the lower layer in the cell was drainedthrough the bottom of the cell, weighed 265 g (58% yield).

To the fluorocarbons thus separated, were added equal volumes of 70%aqueous potassium hydroxide solution and diisobutylamine, and theresulting mixture was refluxed for about five days. The reaction mixturewas then cooled in an ice bath, and filtered by suction. Theperfluoro-compounds sedimented in the lowermost layer were separated ina separatory funnel, washed successively with diluted sulfuric acid,concentrated sulfuric acid, saturated aqueous sodium hydrogen carbonatesolution, 90% aqueous acetone solution containing 3% of potassiumiodide, and water to yield 110 g of a transparent perfluoro-compoundscontaining no protons. This was distilled on a fractional distillationapparatus equipped with a spinning band column to afford 33 g (7% yield)of the desired product boiling at 143°-152° C. This product wascollected, purified, and then analyzed by infrared absorptionspectrometry, ¹⁹ F-nuclear magnetic resonance spectrometory and massspectrometory, and was confirmed to be the objective compound,perfluoro-2-azatricyclo[5,3,1,0²,6 ]-undecane of which chemicalstructure is shown in Table 1 as compound No. 1.

EXAMPLES 2-134

A series of other perfluorotricyclic amine compounds having the formulas(II and V), wherein j is 1 was synthesized from perhydrotricyclic aminecompounds each corresponding thereto and purified in the same manner asthat described above and each product was confirmed to be the objectivecompound upon analysis by infrared absorption spectrometory, ¹⁹F-nuclear magnetic resonance spectrometory and mass spectrometory.

The structural formula and the boiling point of each of the objectivecompounds as well as the starting compounds are shown in the Table 1.The symbol "F-" in the structural formula indicates that the compound isperfluorinated. For example, the formula ##STR7## indicates in its exactmeaning the formula ##STR8##

                  TABLE 1                                                         ______________________________________                                                                              Boil-                                                                         ing                                          Starting     Objective           pt.                                     No.  compound     compound            (°C.)                            ______________________________________                                        1    2-Azatricyclo- [5,3,1,0.sup.2,6 ]- undecane                                                                    143- 152                                2    1-Methyl-2-aza- tricyclo[5,3,1, 0.sup.2,6 ]undecane                                         ##STR9##           154- 165                                 3   3-Methyl-2-aza- tricyclo[5,3,1, 0.sup.2,6 ]undecane                                         ##STR10##          156- 166                                 4   4-Methyl-2-aza- tricyclo[5,3,1, 0.sup.2,6 ]undecane                                         ##STR11##          156- 167                                 5   5-Methyl-2-aza- tricyclo[5,3,1, 0.sup.2,6 ]undecane                                         ##STR12##          156- 167                                 6    6-Methyl-2-aza- tricyclo[5,3,1, 0.sup.2,6 ]undecane                                        ##STR13##          155- 166                                 7   7-Methyl-2-aza- tricyclo[5,3,1, 0.sup.2,6 ]undecane                                         ##STR14##          155- 167                                 8   8-Methyl-2-aza- tricyclo[5,3,1, 0.sup.2,6 ]undecane                                         ##STR15##          156- 167                                 9   9-Methyl-2-aza- tricyclo[5,3,1, 0.sup.2,6 ]undecane                                         ##STR16##          156- 167                                 10  10-Methyl-2-aza- tricyclo[5,3,1, 0.sup.2,6 ]undecane                                        ##STR17##          156- 168                                 11  11-Methyl-2-aza- tricyclo[5,3,1, 0.sup.2,6 ]undecane                                        ##STR18##          155- 166                                 12  2-Azatricyclo-  [6,3,1,0.sup.2,7 ]- dodecane                                                ##STR19##          154- 166                                 13  2-Azatricyclo- [6,3,1,0.sup.2,6 ]- dodecane                                                 ##STR20##          155- 166                                 14  3-Azatricyclo- [6,3,1,0.sup.3,7 ]- dodecane                                                 ##STR21##          155- 166                                 15  2-Azatricyclo- [7,3,1,0.sup.2,6 ]- tridecane                                                ##STR22##          167- 177                                 16  2-Azatricyclo- [7,3,1,0.sup.2,7 ]- tridecane                                                ##STR23##          167- 177                                 17  2-Azatricyclo- [7,3,1,0.sup.2,8 ]- tridecane                                                ##STR24##          167- 177                                 18  3-Azatricyclo- [7,3,1,0.sup.3,7 ]- tridecane                                                ##STR25##          166- 176                                 19  3-Azatricyclo- [7,3,1,0.sup.3,8 ]- tridecane                                                ##STR26##          167- 177                                 20  4-Azatricyclo- [7,3,1,0.sup.4,8 ]- tridecane                                                ##STR27##          167- 177                                 21  2-Azatricyclo- [6,4,0,1.sup.2,6 ]- dodecane                                                 ##STR28##          155- 167                                 22  2-Azatricyclo- [6,4,1,0.sup.2,7 ]- tridecane                                                ##STR29##          167- 178                                 23  2-Azatricyclo- [6,4,0,1.sup.2,7 ]- tridecane                                                ##STR30##          167- 177                                 24  3-Azatricyclo- [6,4,0,1.sup.3,8 ]- tridecane                                                ##STR31##          167-  177                                25  2-Azatricyclo- [6,2,1,2.sup.2,7 ]- undecane                                                 ##STR32##          143- 153                                 26  1-Methyl-2-aza- tricyclo[6,2,1, 0.sup.2,7 ]undecane                                         ##STR33##          155- 165                                 27  3-Methyl-2-aza- tricyclo[6,2,1, 0.sup.2,7 ]undecane                                         ##STR34##          156- 166                                 28  4-Methyl-2-aza- tricyclo[6,2,1, 0.sup.2,7 ]-undecane                                        ##STR35##          156- 167                                 29  5-Methyl-2-aza- tricyclo[6,2,1, 0.sup.2,7 ]undecane                                         ##STR36##          155- 167                                 30  6-Methyl-2-aza- tricyclo[6,2,1, 0.sup.2,7 ]undecane                                         ##STR37##          156- 166                                 31  7-Methyl-2-aza- tricyclo[6,2,1, 0.sup.2,7 ]undecane                                         ##STR38##          155- 166                                 32  8-Methyl-2-aza- tricyclo[6,2,1, 0.sup.2,7 ]undecane                                         ##STR39##          155- 165                                 33  9-Methyl-2-aza- tricyclo[6,2,1, 0.sup.2,7 ]-undecane                                        ##STR40##          156- 166                                 34  10-Methyl-2-aza- tricyclo[6,2,1, 0.sup.2,7 ]undecane                                        ##STR41##          156- 166                                 35  11-Methyl-2-aza- tricyclo[6,2,1, 0.sup.2,7 ]undecane                                        ##STR42##          155- 167                                 36  2-azatricyclo- [6,2,1,0.sup.2,6 ]- undecane                                                 ##STR43##          143- 153                                 37  1-Methyl-2-aza- tricyclo[ 6,2,1, 0.sup.2,6 ]undecane                                        ##STR44##          155- 166                                 38  3-Methyl-2-aza- tricyclo[6,2,1, 0.sup.2,6 ]undecane                                         ##STR45##          156- 166                                 39  4-Methyl-2-aza- tricyclo[6,2,1, 0.sup.2,6 ]undecane                                         ##STR46##          156- 167                                 40  5-Methyl-2-aza- tricyclo[6,2,1, 0.sup.2,6 ]undecane                                         ##STR47##          156- 167                                 41  6-Methyl-2-aza- tricyclo[6,2,1, 0.sup.2,6 ]undecane                                         ##STR48##          155- 166                                 42  7-Methyl-2-aza- tricyclo[6,2,1, 0.sup.2,6 ]undecane                                         ##STR49##          155- 166                                 43  8-Methyl-2-aza- tricyclo[6,2,1, 0.sup.2,6 ]undecane                                         ##STR50##          155- 166                                 44  9-Methyl-2-aza- tricyclo[6,2,1, 0.sup.2,6 ]undecane                                         ##STR51##          156- 166                                 45  10-Methyl-2-aza- tricyclo[6,2,1, 0.sup.2,6 ]undecane                                        ##STR52##          156- 167                                 46  11-Methyl-2-aza- tricyclo[6,2,1, 0.sup.2,6 ]undecane                                        ##STR53##          156- 167                                 47  3-Azatricyclo- [6,2,1,0.sup.3,7 ]- undecane                                                 ##STR54##          143- 154                                 48  1-Methyl-3-aza- tricyclo[6,2, 1,0.sup.3,7 ]undecane                                         ##STR55##          156- 166                                 49  2-Methyl-3-aza- tricyclo[6,2,1, 0.sup.3,7 ]undecane                                         ##STR56##          157- 167                                 50  4-Methyl-3-aza- tricyclo[6,2,1, 0.sup.3,7 ]undecane                                         ##STR57##          157- 166                                 51  5-Methyl-3-aza- tricyclo[6,2,1, 0.sup.3,7 ]undecane                                         ##STR58##          157- 167                                 52  6-Methyl-3-aza- tricyclo[6,2,1, 0.sup.3,7 ]undecane                                         ##STR59##          157- 167                                 53  7-Methyl-3-aza- tricyclo[6,2,1, 0.sup.3,7 ]undecane                                         ##STR60##          156- 166                                 54  8-Methyl-3-aza- tricyclo[6,2,1, 0.sup.3,7 ]undecane                                         ##STR61##          156- 167                                 55  9-Methyl-3-aza- tricyclo[6,2,1, 0.sup.3,7 ]undecane                                         ##STR62##          157- 166                                 56  10-Methyl-3-aza- tricyclo[6,2,1, 0.sup.3,7 ]undecane                                        ##STR63##          157- 167                                 57  11-Methyl-3-aza- tricyclo[6,2,1, 0.sup.3,7 ]undecane                                        ##STR64##          157- 166                                 58  2-Azatricyclo- [7,2,1,0.sup.2,6 ]- dodecane                                                 ##STR65##          156- 167                                 59  2-Azatricyclo- [7,2,1,0.sup.2,7 ]- dodecane                                                 ##STR66##          156- 166                                 60  2-Azatricyclo- [7,2,1,0.sup.2,8 ]- dodecane                                                 ##STR67##          156- 166                                 61  3-Azatricyclo- [7,2,1,0.sup.3,7 ]- dodecane                                                 ##STR68##          155-  165                                62  3-Azatricyclo- [7,2,1,0.sup.3,8 ]- dodecane                                                 ##STR69##          156- 166                                 63  4-Azatricyclo- [7,2,1,0.sup.4,8 ]- dodecane                                                 ##STR70##          155- 166                                 64  2-Azatricyclo- [8,2,1,0.sup.2,6 ]- tridecane                                                ##STR71##          168- 177                                 65  2-Azatricyclo- [8,2,1,0.sup.2,7 ]- tridecane                                                ##STR72##          167- 177                                 66  2-Azatricyclo- [8,2,1,0.sup.2,8 ]- tridecane                                                ##STR73##          167- 178                                 67  2-Azatricyclo- [8,2,1,0.sup.2,9 ]- tridecane                                                ##STR74##          166- 178                                 68  3-Azatricyclo- [8,2,1,0.sup.3,7 ]-  tridecane                                               ##STR75##          167- 178                                 69  3-Azatricyclo- [8,2,1,0.sup.3,8 ]- tridecane                                                ##STR76##          166- 177                                 70  3-Azatricyclo- [8,2,1,0.sup.3,9 ]- tridecane                                                ##STR77##          167- 177                                 71  4-Azatricyclo- [8,2,1,0.sup.4,8 ]- tridecane                                                ##STR78##          167- 178                                 72  4-Azatricyclo- [8,2,1,0.sup.4,9 ]- tridecane                                                ##STR79##          167- 177                                 73  5-Azatricyclo- [8,2,1,0.sup.5,9 ]- tridecane                                                ##STR80##          166- 176                                 74  2-Azatricyclo- [5,2,1,0.sup.2,6 ]- decane                                                   ##STR81##          120- 130                                 75  1-Methyl-2-aza- tricyclo[5,2,1, 0.sup.2,6 ]-decane                                          ##STR82##          142- 153                                 76  3-Methyl-2-aza- tricyclo[5,2,1, 0.sup.2,6 ]decane                                           ##STR83##          143- 153                                 77  4-Methyl-2-aza- tricyclo[5,2,1, 0.sup. 2,6 ]decane                                          ##STR84##          143- 154                                 78  5-methyl-2-aza- tricyclo[5,2,1, 0.sup.2,6 ]decane                                           ##STR85##          143- 154                                 79  6-Methyl-2-aza- tricyclo[5,2,1, 0.sup.2,6 ]decane                                           ##STR86##          142- 153                                 80  7-Methyl-2-aza- tricyclo[5,2,1, 0.sup.2,6 ]decane                                           ##STR87##          142- 154                                 81  8-Methyl-2-aza- tricyclo[5,2,1, 0.sup.2,6 ]decane                                           ##STR88##          143- 154                                 82  9-Methyl-2-aza- tricyclo[5,2,1, 0.sup.2,6 ]decane                                           ##STR89##          143- 154                                 83  10-Methyl-2-aza- tricyclo[5,2,1, 0.sup.2,6 ]decane                                          ##STR90##          144- 154                                 84  1-Ethyl-2-aza- tricyclo[5,2,1, 0.sup.2,6 ]decane                                            ##STR91##          156- 167                                 85  3-Ethyl-2-aza- tricyclo[5,2,1, 0.sup.2,6 ]decane                                            ##STR92##          157- 168                                 86  4-Ethyl-2-aza- tricyclo[5,2,1, 0.sup.2,6 ]decane                                            ##STR93##          157- 167                                 87  5-Ethyl-2-aza- tricyclo[5,2,1, 0.sup.2,6 ]decane                                            ##STR94##          157- 167                                 88  6-Ethyl-2-aza- tricyclo[5,2,1, 0.sup.2,6 ]decane                                            ##STR95##          156- 166                                 89  7-Ethyl-2-aza- tricyclo[5,2,1, 0.sup.2,6 ]decane                                            ##STR96##          156- 166                                 90  8-Ethyl-2-aza- tricyclo[5,2,1, 0.sup.2,6 ]decane                                            ##STR97##          157- 168                                 91  9-Ethyl-2-aza- tricyclo[5,2,1, 0.sup.2,6 ]decane                                            ##STR98##          157- 167                                 92  10-Ethyl-2-za- tricyclo[5,2,1, 0.sup.2,6 ]decane                                            ##STR99##          157- 167                                 93  1,3-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane                                     ##STR100##         156- 167                                 94  1,4-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane                                     ##STR101##         156- 167                                 95  1,5-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane                                     ##STR102##         156- 168                                 96  1,6-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane                                     ##STR103##         155- 165                                 97  1,7-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane                                     ##STR104##         155- 166                                 98  1,8-Dimethyl-2- azatricyclo- [ 5,2,1,0.sup.2,6 ]- decane                                    ##STR105##         156- 167                                 99  1,9-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane                                     ##STR106##         156- 167                                 100 1,10-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane                                    ##STR107##         156- 167                                 101 3,3-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane                                     ##STR108##         157- 167                                 102 3,4-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane                                     ##STR109##         157- 167                                 103 3,5-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane                                     ##STR110##         157- 167                                 104 3,6-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane                                     ##STR111##         156- 166                                 105 3,7-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane                                     ##STR112##         156- 167                                 106 3,8-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane                                     ##STR113##         156- 167                                 107 3,9-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane                                     ##STR114##         157- 167                                 108 3,10-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane                                    ##STR115##         157- 166                                 109  4,4-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane                                    ##STR116##         157- 167                                 110 4,5-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane                                     ##STR117##         156- 167                                 111 4,6-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane                                     ##STR118##         156- 165                                 112 4,7-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane                                     ##STR119##         155- 166                                 113 4,8-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane                                     ##STR120##         156- 167                                 114 4,9-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane                                     ##STR121##         156- 167                                 115 4,10-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane                                    ##STR122##         156- 166                                 116 5,5-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane                                     ##STR123##         156- 167                                 117 5,6-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane                                     ##STR124##         155- 166                                 118 5,7-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane                                     ##STR125##         154- 166                                 119 5,8-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane                                     ##STR126##          157- 168                                120 5,9-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane                                     ##STR127##         157- 167                                 121 5,10-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane                                    ##STR128##         156- 167                                 122 6,7-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane                                     ##STR129##         154- 166                                 123 6,8-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane                                     ##STR130##         155- 167                                 124 6,9-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane                                     ##STR131##         155- 166                                 125 6,10-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ] - decane                                   ##STR132##         156- 165                                 126 7,8-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane                                     ##STR133##         156- 167                                 127 7,9-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane                                     ##STR134##         155- 167                                 128 7,10-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane                                    ##STR135##         154- 166                                 129 8,8-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane                                     ##STR136##         156- 165                                 130 8,9-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane                                     ##STR137##         155- 166                                 131 8,10-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane                                    ##STR138##         156- 166                                 132 9,9-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane                                     ##STR139##         155- 166                                 133 9,10-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane                                    ##STR140##         156- 166                                 134 10,10-Dimethyl-2- azatricyclo- [5,2,1,0.sup.2,6 ]- decane                                   ##STR141##         156- 165                                ______________________________________                                    

EXAMPLES 135-157

A series of perfluorotricyclic amine compounds of the formula (IV)wherein j is 2 or 3 was synthesized, purified and confirmed to be theobjective compound in the same manner as in Example 1.

The structural formula and the boiling point of each of the objectivecompounds are shown in the Table 2. The symbol "F-" in the structuralformula indicates that the compound is perfluorinated. For example, theformula ##STR142## indicates in its exact meaning the formula ##STR143##

                  TABLE 2                                                         ______________________________________                                              Starting     Objective        Boiling                                   No.   compound     compound         pt. (°C.)                          ______________________________________                                        135   2-Azatricyclo- [5,2,2,0.sup.2,6 ]- undecane                                                                 144-155                                   136   1-Methyl-2-aza- tricyclo[5,2,2, 0.sup.2,6 ]undecane                                         ##STR144##      155-166                                    137  3-Methyl-2-aza- tricyclo[5,2,2, 0.sup.2,6 ]undecane                                         ##STR145##      156-167                                    138  4-Methyl-2-aza- tricyclo[5,2,2, 0.sup.2,6 ]undecane                                         ##STR146##      156-167                                    139  5-Methyl-2-aza- tricyclo[5,2,2, 0.sup.2,6 ]undecane                                         ##STR147##      156-168                                    140  6-Methyl-2-aza- tricyclo[5,2,2 0.sup.2,6 ]undecane                                          ##STR148##      155-166                                    141  7-Methyl-2-aza- tricyclo[5,2,2, 0.sup.2,6 ]undecane                                         ##STR149##      155-165                                    142  8-Methyl-2-aza- tricyclo[5,2,2, 0.sup.2,6 ]undecane                                         ##STR150##      156-167                                    143  9-Methyl-2-aza- tricyclo[5,2,2, 0.sup.2,6 ]undecane                                         ##STR151##      156-167                                    144  2-Azatricyclo- [6,2,2,0.sup.2,7 ]- dodecane                                                 ##STR152##      155-165                                    145  2-Azatricyclo- [6,2,2,0.sup.2,6 ]- dodecane                                                 ##STR153##      156-166                                    146  3-Azatricyclo- [6,2,2,0.sup.3,7 ]- dodecane                                                 ##STR154##      156-166                                    147  2-Azatricyclo- [7,2,2,0.sup.2,6 ]- tridecane                                                ##STR155##      167-176                                    148  2-Azatricyclo- [7,2,2,0.sup.2,7 ]- tridecane                                                ##STR156##      166-177                                    149  2-Azatricyclo- [7,2,2,0.sup.2,8 ]- tridecane                                                ##STR157##      165-176                                    150  3-Azatricyclo- [7,2,2,0.sup.3,7 ]- tridecane                                                ##STR158##      166-177                                    151  3-Azatricyclo- [7,2,2,0.sup.3,8 ]- tridecane                                                ##STR159##      166-176                                    152  4-Azatricyclo- [7,2,2,0.sup.4,8 ]- tridecane                                                ##STR160##      164-177                                    153  2-Azatricyclo- [5,3,2,0.sup.2,6 ]- dodecane                                                 ##STR161##      156-165                                    154  2-Azatricyclo- [6,3,2,0.sup.2,6 ] - tridecane                                               ##STR162##      166-176                                    155  2-Azatricyclo- [6,3,2,0.sup.2,7 ]- tridecane                                                ##STR163##      166-176                                    156  3-Azatricyclo- [6,3,2,0.sup.3,7 ]- tridecane                                                ##STR164##      166-177                                    157  2-Azatricyclo- [5,3,3,0.sup.2,6 ]- tridecane                                                ##STR165##      165-176                                   ______________________________________                                    

EXAMPLES 158-201

A series of perfluorotricyclic amine compounds of the formula (III)wherein j is zero was synthesized, purified and confirmed to be theobjective compound in the same manner as in Example 1.

The structural formula and the boiling point of each of the objectivecompounds is shown in the Table 3. The symbol "F-" in the structuralformula indicates that the compound is perfluorinated. For example, theformula ##STR166## indicates in its exact meaning the formula ##STR167##

                  TABLE 3                                                         ______________________________________                                                                              Boil-                                                                         ing                                          Starting    Objective            pt.                                     No.  compound    compound             (°C.)                            ______________________________________                                        158  1-Azatricyclo- [6,3,0,0.sup.2,6 ]- undecane                                                                    143- 153                                159  2-Methyl-1-aza- tricyclo[6,3,0, 0.sup.2,6 ]undecane                                        ##STR168##          155- 165                                  160                                                                              3-Methyl-1-aza- tricyclo[6,3,0, 0.sup.2,6 ]undecane                                        ##STR169##          155- 166                                 161 4-Methyl-1-aza- tricyclo[6,3,0, 0.sup.2,6 ]undecane                                        ##STR170##          156- 166                                 162 5-Methyl-1-aza- tricyclo[6,3,0, 0.sup.2,6 ]undecane                                        ##STR171##          155- 166                                 163 6-Methyl-1-aza- tricyclo[6,3,0, 0.sup.2,6 ]undecane                                        ##STR172##          155- 165                                 164 7-Methyl-1-aza- tricyclo[6,3,0, 0.sup.2,6 ]undecane                                        ##STR173##          156- 166                                 165 8-Methyl-1-aza- tricyclo[6,3,0, 0.sup.2,6  undecane                                        ##STR174##          154- 166                                 166 9-Methyl-1-aza- tricyclo[6,3,0, 0.sup.2,6 ]undecane                                        ##STR175##          155- 165                                  167                                                                              10-Methyl- 1-aza- tricyclo[6,3,0, 0.sup.2,6 ]undecane                                      ##STR176##          155- 165                                 168 11-Methyl- 1-aza- tricyclo[6,3,0, 0.sup.2,6 ]undecane                                      ##STR177##          155- 166                                 169 1-Azatricyclo- [6,3,0,0.sup.3,7 ]- undecane                                                ##STR178##          143- 154                                 170 2-Methyl-1-aza- tricyclo- [6,3,0,0.sup.3,7 ]- undecane                                     ##STR179##          156- 166                                 171 3-Methyl-1-aza- tricyclo- [6,3,0,0.sup.3,7 ]- undecane                                     ##STR180##          154- 165                                 172 4-Methyl-1-aza- tricyclo- [6,3,0,0.sup.3,7 ]- undecane                                     ##STR181##          155- 165                                 173 5-Methyl-1-aza- tricyclo- [6,3,0,0.sup.3,7 ]- undecane                                     ##STR182##          155-  165                                 174                                                                              6-Methyl-1-aza- tricyclo- [6,3,0,0.sup.3,7]- undecane                                      ##STR183##          155- 166                                 175 7-Methyl-1-aza- tricyclo- [6,3,0,0.sup.3,7 ]- undecane                                     ##STR184##          154- 165                                 176 8-Methyl-1-aza- tricyclo- [6,3,0,0.sup.3,7 ]- undecane                                     ##STR185##          154- 166                                 177 9-Methyl-1-aza- tricyclo- [6,3,0,0.sup.3,7 ]- undecane                                     ##STR186##          156- 166                                 178 10-Methyl- 1-aza- tricyclo- [6,3,0,0.sup.3,7 ]- undecane                                   ##STR187##          155-  165                                179 11-Methyl- 1-aza- tricyclo- [6,3,0,0.sup.3,7 ]- undecane                                   ##STR188##          155- 164                                 180 1-Azatricyclo- [7,3,0,0.sup.2,7 ]- dodecane                                                ##STR189##          154- 165                                 181 1-Azatricyclo- [7,3,0,0.sup.2,6 ]- dodecane                                                ##STR190##          155- 165                                 182 1-Azatricyclo- [7,3,0,0.sup.3,7 ]- dodecane                                                ##STR191##          155- 166                                 183 1-Azatricyclo- [7,3,0,0.sup.3,8 ]- dodecane                                                ##STR192##          154- 165                                 184 1-Azatricyclo- [7,3,0,0.sup.4,8 ]- dodecane                                                ##STR193##          153- 165                                  185                                                                              2-Azatricyclo- [7,3,0,0.sup.2,7 ]- dodecane                                                ##STR194##          154- 165                                 186 3-Azatricyclo- [7,3,0,0.sup.3,8 ]- dodecane                                                ##STR195##          154- 165                                 187 1-Azatricyclo- [8,3,0,0.sup.2,8 ]- tridecane                                               ##STR196##          166- 177                                 188 1-Azatricyclo- [8,3,0,0.sup.2,7 ]- tridecane                                               ##STR197##          165- 177                                 189 1-Azatricyclo- [8,3,0,0.sup.2,6 ]- tridecane                                               ##STR198##          166- 176                                  190                                                                              1-Azatricyclo- [8,3,0,0.sup.3,9 ]- tridecane                                               ##STR199##          166-  176                                191 1-Azatricyclo- [8,3,0,0.sup.3,8 ]- tridecane                                               ##STR200##          165- 175                                 192 1-Azatricyclo- [8,3,0,0.sup.3,7 ]- tridecane                                               ##STR201##          166- 176                                 193 1-Azatricyclo- [8,3,0,0.sup.4,9 ]- tridecane                                               ##STR202##          165- 176                                 194 1-Azatricyclo- [8,3,0,0.sup.4,8 ]- tridecane                                               ##STR203##          165- 175                                  195                                                                              1-Azatricyclo- [7,4,0,0.sup.2,7 ]- tridecane                                               ##STR204##          164- 175                                 196 1-Azatricyclo- [7,4,0,0.sup.2,6 ]- tridecane                                               ##STR205##          165- 176                                 197 1-Azatricyclo- [7,4,0,0.sup.3,7 ] tridecane                                                ##STR206##          164- 174                                 198 1-Azatricyclo- [7,4,0,0.sup.3,8 ]- tridecane                                               ##STR207##          165- 175                                 199 4-Azatricyclo- [8,3,0,0.sup.4,9 ]- tridecane                                               ##STR208##          166- 176                                 200 2-Azatricyclo- [8,3,0,0.sup.2,8 ]- tridecane                                               ##STR209##          165- 175                                 201 3-Azatricyclo- [8,3,0,0.sup.3,9 ]- tridecane                                               ##STR210##          165- 175                                ______________________________________                                    

What is claimed is:
 1. A perfluoro compound represented by the formula,##STR211## wherein k, j, l and m are zero or an integer of from 1 to 3,and n is an integer of from 1 to 3, the rings A, B and C beingoptionally substituted with at least one trifluoromethyl group.
 2. Aperfluoro compound of claim 1, of which formula is ##STR212## wherein kis an integer of 1 or 2; l, m and n are zero or an integer of 1 or 2,any member of the formula being optionally substituted with at least onetrifluoromethyl group.
 3. A perfluoro compound of claim 1, of whichformula is ##STR213## wherein k and n are an integer of 1, 2 or 3; l andm are zero or an integer of 1, 2 or 3, any member of the formula beingoptionally substituted with at least one trifluoromethyl group.
 4. Aperfluoro compound of claim 1, of which formula is ##STR214## wherein kand j are zero or an integer of 1, l, m and n are zero or an integer of1 or 2, any member of the formula being optionally substituted with atleast one trifluoromethyl group.
 5. A perfluoro compound of claim 1, ofwhich formula is ##STR215## wherein l and m are zero or an integer of 1,2 or 3; n is an integer of 1, 2 or 3, any member of the formula beingoptionally substituted with at least one trifluoromethyl group.
 6. Aperfluoro compound of claim 1 which has 9 to 12 carbon atoms.
 7. Acomposition for use as a blood substitute or infusion fluid whichcomposition is an aqueous emulsion of a perfluoro compound as defined inclaim
 1. 8. A composition according to claim 7, which contains from 5 to50% (w/v) of the perfluoro compound as defined in claim 1, and asemulsifier, a nonionic surfactant and/or phospholipid.